P-nitro-o-trifluoromethyl benzeneazo-n-beta-cyanoethyl-n-hydroxyalkylaniline dye compounds



Patented Jan. 3, 1950 P-NITRO-O-TRIFLUOROMETHYL BENZENE- AZO-N B CYANOETHYL-N-HYDROXYAL- KYLANILINE DYE COMPOUNDS Joseph B. Dickey, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application July 26, 1946, Serial No. 686,439

3 Claims.

This invention relates to new azo compounds and their application to the art of dyeing or coloring textile materials, such as filaments, threads, yarns or fabrics (knitted or Woven) comprising a cellulose carboxylic ester.

I have discovered that the azo compounds having the general formula:

wherein R stands for the p-hydroxyethyl group, the p-hydroxypropyl group or the Y-hydroxypropyl group are unusually valuable dyes for col- CHZOHQCN oring textile materials comprising cellulose carwhich is one of the best, if not the best, scarlet azo dyes now available for dyeing cellulose acetate textile materials.

Further, I have found that the dye compounds of my invention yield dyeings on cellulose acetate textile materials which are of greatly superior light iastness (usually 3 to 5 times) to the dyeings obtained on cellulose acetate textile materials with the dye having the formula:

OHQCHZOH the dye having the formula:

crooner-lemon No O CH CH ON Fa or the dyes having the general formula:

wherein X stands for a hydrogen atom, a chlorine atom, a bromine atom, a methyl group or a methoxy group, Z stands for a hydrogen atom, a methyl group, a methoxy group or an acetylamino group, R1 stands for a p-hydroxyethyl group, a p-hydroxypropyl group, a v-hydroxypropyl group or a p,Y-dihydroxypropyl group and R2 stands for a B-cyanoethyl group, a methyl group, an ethyl group or a ,e-hydroxyethyl group.

In addition, the aqueous nitrous acid fastness properties of the dyeings obtained on cellulose acetate with the new dye compounds of the invention are considerably superior to that of the dyeings obtained with the scarlet azo dyes now available for dyeing cellulose acetate, as for example, p-nitrobenzeneazo-N-ethyl-N-p-hydroxyethylaniline, previously referred to. The advantages of my new dye compounds could not have been predicted.

It is an object of my invention to provide new azo dye compounds. Another object is to provide a satisfactory process for the preparation of the new azo dye compounds of my invention. A further object is to provide cellulose carboxylic ester textile materials colored with the new azo compounds of the invention. A particular object is to provide dyed cellulose acetate textile materials of outstanding iastness to light and gas.

The new azo dye compounds of my invention can be prepared by diazotizing l-amino-Z-trifluoromethyl-4-nitrobenzene and coupling the diazonium salt obtained with a compound having the formula:

\CH2CHZCN wherein R stands for the ,e-hydroxyethyl group, the p-hydroxypropyl group or the Y-hydroxypropyl group.

The following examples, in which parts are by weight, illustrate the compounds of the invention and the manner in which they can be prepared.

Example 1.--Preparati0n of p-nitro-o-trz'fluoromethylbenzeneazo N ,B-cyanoethyZ-N-p-hydromyethylam'line 3.8 parts of dry sodium nitrite are added slowly with stirring to 135 parts of sulfuric acid (sp. gr. 1.83) while maintaining the temperature of the reaction mixture below C. When the sodium nitrite is completely dissolved, the reaction mixture is cooled to 10-15 C. and 10.3 parts of dry powdered l-amino-2-trifluoromethyl-4-nitrobenzene are added over a period of 15-20 minutes While maintaining the temperature below 25 C. The reaction mixture is stirred until all of the l-amino 2 trifluoromethyl 4 nitrobenzene is completely broken up and disazotized (approximately 1 hour). 05 part of powdered suliamic acid are added to destroy any excess nitrous acid present in the reaction mixture.

9.5 grams of N-o-hydroxyethyl-N-p-cyanoethylaniline are dissolved in; 162: parts of l2 aqueous sulfuric acid. The reaction mixture resulting is cooled to 0-10 C. by adding 400 parts of crushed ice with stirring. The diazo solutionprepared as described above is, then added slowlywith stirring. Coupling takes place immediately. Throughout the coupling reaction the tempera ture should be maintained at C. or below and ice should be added as necessary to so maintain the temperature. Upon completion of thecou-. pling reaction, the reaction mixture is permitted to stand for /2, hqurafterwhiclrit i slowly made neutral. to Con red paper; y th addit n; of sodium carbonate and then allowed; to stand for one hour. The dye compound formed is recovered by filtration, washed well with water and dried. It has the formula:

CEa

and dyes cellulose acetate textile materials scarlet shades from an aqueous, suspension.

Example 2.Prepa ration 01f p-nitro-o-trz'fluoromethylbenzeneazo N B cyanoethyl-N-e-hydrorypropylaniline CHZCHOHCHQ It colors cellulose acetate textile materials scarlet shades.

Example 3.-Preparatz'on of p-nitro-o-trifluoromethylbenzeneazo N e-cyanoethyZ-N-y-hydroxypropylaniline This dye compound is prepared by substituting'9.'7 gramsof N-'y-hydroxypropyl-N-,8-cyanoethylaniline for- N.-o-hydroxyethyl-N:-o-cyanoethylaniline in the reaction describedinExample 1-. The diazotization, coupling and dye recovery operations are carried out in accordance with the procedure described in-Example 1'. The dye compound obtained has, the formula:

CHzCHzCH'gOH Itdyes, cellulose acetate textile material scarlet shades.

In order; that the; preparation; of; the dye compoundso im nv n io may be nt r yle r. th prepar tion he ou ine ompone ts. ed. in their manufacture is described hereinafter.

, umn (e. g. a Penn State column).

Preparation of N-B-cyanoethyZ-N-p-hydroxy ethylam'lz'ne 123 grams oi N-p-hydroxyethylaniline, 53 grams of acrylonitrile and 10 cc. of glacial acetic acid are placed in a round-bottom flask and heated on a steam bath under a reflux condenser for 150 hours. The reaction mixture is then distilled through an. eflicient fractionating col- 154 grams of N fi-cyanoethyl-N-,B-hydroxyethylaniline boiling at 205-20? C./8-, mm. are obtained. By the substitution of, an equivalent gram molecular weight. of N-p-hydroxypropylaniline and N-7- hydroxypropylaniline for the N-fi-hydroxyethylaniline of the foregoing example, N-p-cyanoethyl N-[i-hydroxypropylaniline and N-fi-cyanoethyl-N-y-hydroxypropylaniline, respectively, are obtained.

l-arnino -.v 2 trifiuQromethyl-lrnitrobenzene (known also as 5-nitro-2@aminorbenzotrifluoride) is a known compound-and accordingly a description of its preparation is deemed, unnecessary.

Cellulose carboxylic esters, which, are employed in the manufacture of textile materials, include the partially hydrolysedas. Well as the unhydrolysed cellulose acetates, cellulose propionates and cellulose butyrates' and the partially hydrolysed as well as theunhydrolyzed' mixed estersof cellulose, such as cellulose acetate-propi'onate and cellulose acetate-butyrate. All of these cellulose carboxylic esters. consist, of a cellulose portion or radical and an acid radical which contains from 2 to 4. carbon atoms.

The azo, dye compounds of; my inventioncan be applied. to. the. textile materials indicated hereinbefore in the, form of an aqueonsdispersion and are ordinarily; so. applied. To; illustrate, the dye compound is finely ground with a dispersing agent such as. Turkey red oil; sulflte; cellulose solution, soap, or an oleyl glyceryli suliate and the resulting paste is. dispersed.- in water. The dye bath thus prepared is. heated to a temperature approximating 45f- C:-55.' C; and the textile material to. be dyed; is-immersed in. the dyebath, following which. the: temperature is; gradually raised, to C.- C. and maintained at this point until dyeing is complete, usually one half hour to two hours. Upon completion of the dyeing operationthe textile material is removed from the dyebath, washed. with, soap, rinsed well with water and dried;

AS the azo dy compounds of: the invention possess; good; afilnity: for. the; textile. materials named: herein. and, dye these materials readily (LIE;

wherein R stands, for a member selected from the group consisting of the B-hydroxyethyl group and the -hydroxypropyl group.

CHzOHgCN 2. The azo dye compound having the general formula:

Number 3. The azo dye compound having the general formula:

2,194,926 2,194,927 CmcmoHwH 2,337,987

CH CH CN F; 2 a Number JOSEPH B. DICKEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Engelmann Apr. 80, 1935 Holzach et a1 Feb. 22, 1938 Heyna Apr. 4, 1939 Hitch Sept. 12, 1939 Daudt Mar. 26, 1940 Daudt Mar. 26, 1940 Felix Oct. 30, 1945 FOREIGN PATENTS Country Date Switzerland Dec. 15, 1938 Germany Jan. 4, 1937 

1. THE AZO DYE COMPOUNDS HAVING THE GENERAL FORMULA: 